US7038093B2 - Integrated process for the preparation of phenol from benzene with recycling of the by-products - Google Patents

Integrated process for the preparation of phenol from benzene with recycling of the by-products Download PDF

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Publication number
US7038093B2
US7038093B2 US10/716,460 US71646003A US7038093B2 US 7038093 B2 US7038093 B2 US 7038093B2 US 71646003 A US71646003 A US 71646003A US 7038093 B2 US7038093 B2 US 7038093B2
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benzene
phenol
process according
ranging
weight
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US20040122264A1 (en
Inventor
Daniele Bianchi
Rossella Bortolo
Roberto Buzzoni
Alberto Cesana
Leonardo Dalloro
Rino D'Aloisio
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Versalis SpA
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Polimeri Europa SpA
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Assigned to POLIMERI EUROPA S.P.A. reassignment POLIMERI EUROPA S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BIANCHI, DANIELE, BORTOLO, ROSSELLA, BUZZONI, ROBERTO, CESANA, ALBERTO, DALLORO, LEONARDO, D'ALOISIO, RINO
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to an integrated process for the synthesis of phenol from benzene by the direct oxidation of benzene with hydrogen peroxide, in the presence of a zeolitic catalyst TS-1 and recycling of the by-products.
  • the invention relates to a process for the preparation of phenol wherein the reaction by-products are selectively transformed into phenol and recycled in the process streams.
  • Phenol is an extremely important industrial intermediate used, for example, in the production of polycarbonates or other phenolic resins.
  • Phenol is currently produced industrially starting from cumene.
  • European patent application EP A 919531 describes the use of a specific solvent such as sulfolane for obtaining significant improvements in the conversion and selectivity of these processes (EP A 919531). Alternatively, improvements in conversion and selectivity can also be obtained by activation of the catalyst with hydrogen peroxide and fluorine ions, as described in European patent application EP A 958861.
  • Italian patent application MI 2001A 002410 describes a process which operates in a three-phase reaction system consisting of a solid catalyst/aqueous phase/organic phase (aromatic compound+solvent) which, with respect to the biphasic system, allows the productivity of the oxidation process of benzene to be increased without jeopardizing the selectivity.
  • the process of the invention envisages integration of the synthesis process of phenol with a hydrodeoxygenation section of the by-products, hydroquinone and catechol, which are selectively transformed into phenol and recycled in the process streams and the running of the synthesis section of phenol under particular operating conditions.
  • the object of the present invention relates to a process for the preparation of phenol comprising the following phases:
  • the preparation of phenol by the direct oxidation of benzene ( FIG. 1 , section a) is carried out in a reactor into which benzene, the solvent, water, the catalyst and hydrogen peroxide are fed and where an organic phase is obtained, containing the solvent, non-reacted benzene, water, phenol and by-products (catechol, hydroquinone and phenolic tars).
  • the three-phase reaction system is reached when operating with a controlled quantity of water which is such as to cause a demixing of the liquid phase and prevent the aggregation of the catalyst.
  • the oxidation reaction of benzene is conveniently carried out with a concentration of water ranging from 5 to 50% by weight, concentrations ranging from 15 to 40% are preferably used.
  • the organic solvent can be selected from solvents which are commonly used in the oxidation processes described in the known art such as, for example, methanol, ethanol, isopropyl alcohol, acetone, methylethylketone, acetic acid or acetonitrile.
  • the solvent is used in quantities ranging from 20 to 80% by weight with respect to the reaction mixture.
  • Quantities ranging from 40 to 70% are preferably used.
  • the catalysts used in the oxidation reactor of the present invention are selected from those having general formula (I); x TiO 2 .(1 ⁇ x )SiO 2 (I) wherein: x ranges from 0.0001 to 0.04, preferably from 0.02 to 0.03.
  • the above titanium silicalites can be prepared according to the method described in U.S. Pat. No. 4,410,501 which also specifies their structural characteristics.
  • the titanium silicalites can also be subjected to activation treatment as described in patent EP A 958861.
  • Titanium silicalites in which part of the titanium is substituted by other metals such as boron, aluminum, iron or gallium, can also be used.
  • the catalyst is generally used in quantities ranging from 2 to 60% by weight with respect to the aromatic substrate.
  • Quantities of catalyst ranging from 5 to 40% by weight with respect to the aromatic substrate are preferably used.
  • the hydrogen peroxide is added to the reaction mixture in quantities ranging from 10 to 70% in moles with respect to the aromatic substrate, preferably between 20 and 60% in moles.
  • Solutions of hydrogen peroxide are conveniently used at a concentration ranging from 10 to 60% by weight, preferably from 15 to 60% by weight.
  • the benzene is normally used in quantities ranging from 10 to 80% by weight with respect to the reaction mixture.
  • Quantities of benzene ranging from 15 to 50% by weight with respect to the reaction mixture are preferably used.
  • the oxidation reaction is carried out at temperatures ranging from 500 to 110° C., preferably from 700 to 100° C.
  • the reaction time necessary for the complete use of the hydrogen peroxide depends on the reaction conditions used.
  • the oxidation process described in the present invention can be carried out in reactors of the semibatch type (with the feeding of hydrogen peroxide) or of the CSTR type (continuous stirred batch reactor) with feeding in continuous of the hydrogen peroxide and benzene/solvent mixture.
  • the aqueous phase (in which the catalyst is selectively distributed), is maintained inside the reactor removing the organic phase in a quiet, unstirred zone in which the demixing is effected. In this way, only one phase containing: an aromatic compound, a solvent, a hydroxy-aromatic compound and by-products, is obtained at the outlet.
  • the separation and recovery of the light components of the reaction mixture coming from the oxidation section is carried out by means of fractionated distillation.
  • the azeotropic mixture of benzene/water is obtained at the head in a first column ( FIG. 1 , section b) together with a mixture of solvent, phenol and by-products (catechols, hydroquinone, phenolic tars) at the tail.
  • This mixture is sent to a second distillation column ( FIG. 1 , section c) where purified phenol is obtained at the head and a mixture of solvent and by-products at the tail.
  • the by-products (catechol, hydroquinone and phenolic tars) are separated from the reaction solvent (preferably sulfolane) by means of the procedure described in Italian patent application MI 2002A 001187, which comprises the following phases:
  • the by-products obtained from the recovery section ( FIG. 1 , section g) are then transformed into phenol by means of hydrodeoxygenation with hydrogen ( FIG. 1 , section h).
  • WHSV Weight Hourly Space Velocity, expressed in kg of Benzenediols/h/kg of catalyst
  • the feeding of the reactor consists of a solution of benzenediols in water at a concentration of 5-60% by weight, preferably 10-40% by weight, and hydrogen with a molar ratio with respect to the benzenediols of 2-50, preferably 5-30.
  • the catalyst can be selected from those for hydrodeoxygenation based on elements of group VIB or group VIII of the periodic table.
  • the catalyst when it is based on elements of group VIB, it can contain, as promoters, elements belonging to group VIII and phosphorous.
  • the elements of group VIB can be used in a mixture and, among these, molybdenum and tungsten are preferred.
  • the promoters of group VIII nickel, cobalt, iron and ruthenium are preferred; they can be used in a mixture with each other and with phosphorous.
  • the catalyst when it is based on elements of group VIII, it can contain, as promoters, zinc, rhenium, selenium, tin, germanium and lead.
  • the elements of group VIII can be used in a mixture and, among these, cobalt, palladium, nickel and platinum are preferred.
  • the promoters can also be used in a mixture with each other.
  • the active phase is preferably deposited on a carrier.
  • Preferred carriers are inorganic oxides such as alumina, silica, titanium dioxide, crystalline or amorphous alumino-silicates, crystalline spinels having the general formula F 2+ R 2 3+ O 4 (wherein F 2+ can be Mg, Fe, Zn, Mn, Ni, etc. and R 3+ can be Al, Fe, Cr, etc.) or their mixtures.
  • inorganic oxides such as alumina, silica, titanium dioxide, crystalline or amorphous alumino-silicates, crystalline spinels having the general formula F 2+ R 2 3+ O 4 (wherein F 2+ can be Mg, Fe, Zn, Mn, Ni, etc. and R 3+ can be Al, Fe, Cr, etc.) or their mixtures.
  • catalysts based on an element of group VIB said element is generally present on the carrier in a concentration ranging from 1 to 50% by weight, preferably from 3-30% by weight.
  • the promoters of these catalysts are generally present in concentrations ranging from 0.1 to 100% atomic with respect to the element of group VIB, preferably from 1 to 50%.
  • examples of these catalysts are Mo, W, CoMo, NiMo, NiW, FeMo, RuMo, CoMoP, NiMoP, CoWMo, CoWMoP.
  • these catalysts Before being used in the reaction, these catalysts can be subjected to treatment to modify their chemical characteristics, for example sulfuration with H 2 S, dimethylsulfide, dimethyldisulfide, carbon sulfide or any other compound useful for the purpose.
  • catalysts based on an element of group VIII said element is generally present on the carrier in a concentration ranging from 0.05 to 20% by weight, preferably from 0.1 to 10% by weight.
  • the promoters of these catalysts are generally present in concentrations ranging from 0.5 to 200% atomic with respect to the element of group VIII, preferably from 1 to 120%.
  • examples of these catalysts are Pt, Pd, Co, Ni, PtZn, PtRe, PtNi, PtSe, PtSn, PtGe, PtPb, PdPb, PdSn.
  • reaction temperature can be progressively increased within the range of 250-500° C.
  • the simplified integrated process scheme is provided in FIG. 1 .
  • the solid After cooling, the solid is separated from the mother liquor (pH 4.3) by filtration on a porous septum, then repeatedly washed with deionized water and finally with acetone.
  • the catalyst is subsequently dried under vacuum at 40° C. for 8 hours and then subjected, with a heating rate of 50° C./h, to thermal treatment in air at 550° C. for 4 hours.
  • Titer of the activated catalyst 1.49% of Ti.
  • the dissolved titanium corresponds to 35% by weight.
  • reaction mixture is then cooled to 20° C. and the catalyst is separated by filtration on a porous septum.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 52.0 kg hydroquinone/kg phenol and 78.0 kg catechol/ton phenol.
  • reaction mixture is then cooled to 20° C. and the catalyst is separated by filtration on a porous septum.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 69.9 kg hydroquinone/kg phenol and 104.9 kg catechol/ton phenol.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 117.0 kg hydroquinone/kg phenol and 175.5 kg catechol/ton phenol.
  • Example 3 Operating as described in Example 3, the by-products are subject to hydrogenation obtaining a conversion of catechol and hydroquinone equal to 100%, with a production of 5.47 g (58.2 mmoles) corresponding to a transformation yield to phenol equal to 97%.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 139.8 kg hydroquinone/kg phenol and 209.7 kg catechol/ton phenol.
  • Example 3 Operating as described in Example 3, the by-products are subject to hydrogenation obtaining a conversion of catechol and hydroquinone equal to 100%, with a production of 7.78 g (82.7 mmoles) corresponding to a transformation yield to phenol equal to 97%.
  • reaction mixture is then cooled to 20° C. and the catalyst is separated by filtration on a porous septum.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 76.2 kg hydroquinone/kg phenol and 114.3 kg catechol/ton phenol.
  • Example 3 Operating as described in Example 3, the by-products are subject to hydrogenation obtaining a conversion of catechol and hydroquinone equal to 100% is obtained, with a production of 2.70 g (28.8 mmoles) corresponding to a transformation yield to phenol equal to 97%.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 117.0 kg hydroquinone/kg phenol and 175.5 kg catechol/ton phenol.
  • Example 3 Operating as described in Example 3, the by-products are subject to hydrogenation obtaining a conversion of catechol and hydroquinone equal to 100%, with a production of 5.38 g (57.3 mmoles) corresponding to a transformation yield to phenol equal to 97%.
  • reaction mixture was then evaporated at reduced pressure obtaining only traces of polyphenolic tars as boiler residue.
  • the co-production of by-products is equal to 147.8 kg hydroquinone/kg phenol and 221.7 kg catechol/ton phenol.
  • Example 3 Operating as described in Example 3, the by-products are subject to hydrogenation obtaining a conversion of catechol and hydroquinone equal to 100%, with a production of 8.08 g (85.9 mmoles) corresponding to a transformation yield to phenol equal to 97%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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US10/716,460 2002-11-28 2003-11-20 Integrated process for the preparation of phenol from benzene with recycling of the by-products Expired - Lifetime US7038093B2 (en)

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IT002522A ITMI20022522A1 (it) 2002-11-28 2002-11-28 Processo integrato per la preparazione di fenolo da benzene con riciclo dei sottoprodotti.
ITMI2002A002522 2002-11-28

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EP (1) EP1424320B1 (zh)
JP (1) JP4515079B2 (zh)
KR (1) KR101086652B1 (zh)
CN (1) CN1325455C (zh)
ES (1) ES2436041T3 (zh)
IT (1) ITMI20022522A1 (zh)
RU (1) RU2340591C2 (zh)
TW (1) TWI312721B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070255078A1 (en) * 2004-11-12 2007-11-01 Polimeri Europa S.P.A. Continuous Process for the Preparation of Phenol from Benzene in a Fixed Bed Reactor
US20080144675A1 (en) * 2006-12-13 2008-06-19 Spinelli Luis A Mechanically q-switched co2 laser

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20021187A1 (it) * 2002-05-31 2003-12-01 Polimeri Europa Spa Procedimento per il recupero di fenolo e difenoli
ITMI20050062A1 (it) 2005-01-20 2006-07-21 Polimeri Europa Spa Processo per la preparazione di fenolo
US7915459B2 (en) * 2005-02-24 2011-03-29 Periana Roy A Catalytic systems for the conversion of hydrocarbons to functionalized products
CN106336361A (zh) * 2016-08-24 2017-01-18 安徽金邦医药化工有限公司 一种合成间氨基苯乙醚的方法
CN106349078A (zh) * 2016-08-24 2017-01-25 安徽金邦医药化工有限公司 一种对硝基苯乙醚的催化制备工艺
GB201900553D0 (en) 2019-01-15 2019-03-06 Norwegian Univ Sci & Tech Ntnu Preparation of biofuel from biomass
CN112964509B (zh) * 2021-03-17 2023-03-03 济南市环境研究院 自然界水样原位抽滤及固相萃取集成操作系统及其操作方法

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US4381973A (en) 1980-08-30 1983-05-03 Bayer Aktiengesellschaft Process for the preparation of pyrocatechol and hydroquinone
EP0919531A1 (en) 1997-11-27 1999-06-02 Enichem S.p.A. Process for the oxidation of aromatic compounds to hydroxyaromatic compounds
EP0958861A1 (en) 1998-05-19 1999-11-24 Enichem S.p.A. Activation method of titanium silicalite and its use in oxidation processes with hydrogen peroxide
WO2003042146A1 (en) 2001-11-15 2003-05-22 Polimeri Europa S.P.A. Process for the preparation of hydroxylated aromatic compounds
US20040077906A1 (en) 2002-10-15 2004-04-22 Eni S.P.A. Process for the preparation of phenol by means of the hydrodeoxygenation of benzene-diols

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JP4224877B2 (ja) * 1998-09-11 2009-02-18 三菱化学株式会社 精製フェノールの製造方法
JP3455772B2 (ja) * 1999-09-08 2003-10-14 独立行政法人産業技術総合研究所 フェノール及びその誘導体の回収方法

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US4381973A (en) 1980-08-30 1983-05-03 Bayer Aktiengesellschaft Process for the preparation of pyrocatechol and hydroquinone
EP0919531A1 (en) 1997-11-27 1999-06-02 Enichem S.p.A. Process for the oxidation of aromatic compounds to hydroxyaromatic compounds
US6133487A (en) 1997-11-27 2000-10-17 Enichem S.P.A. Process for the oxidation of aromatic compounds to hydroxyaromatic compounds
EP0958861A1 (en) 1998-05-19 1999-11-24 Enichem S.p.A. Activation method of titanium silicalite and its use in oxidation processes with hydrogen peroxide
WO2003042146A1 (en) 2001-11-15 2003-05-22 Polimeri Europa S.P.A. Process for the preparation of hydroxylated aromatic compounds
US20040077906A1 (en) 2002-10-15 2004-04-22 Eni S.P.A. Process for the preparation of phenol by means of the hydrodeoxygenation of benzene-diols

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070255078A1 (en) * 2004-11-12 2007-11-01 Polimeri Europa S.P.A. Continuous Process for the Preparation of Phenol from Benzene in a Fixed Bed Reactor
US7759529B2 (en) 2004-11-12 2010-07-20 Polimeri Europa S.P.A. Continuous process for the preparation of phenol from benzene in a fixed bed reactor
US20100184593A1 (en) * 2004-11-12 2010-07-22 Polimeri Europa S.P.A. Method to activate a catalyst for a continuous process for the preparation of phenol from benzene in a fixed bed reactor
US8563461B2 (en) 2004-11-12 2013-10-22 Polimeri Europa S.P.A. Method to activate a catalyst for a continuous process for the preparation of phenol from benzene in a fixed bed reactor
US20080144675A1 (en) * 2006-12-13 2008-06-19 Spinelli Luis A Mechanically q-switched co2 laser
US7411989B2 (en) 2006-12-13 2008-08-12 Coherent, Inc. Mechanically Q-switched CO2 laser

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Publication number Publication date
EP1424320B1 (en) 2013-09-11
JP2004175801A (ja) 2004-06-24
US20040122264A1 (en) 2004-06-24
JP4515079B2 (ja) 2010-07-28
KR20040047635A (ko) 2004-06-05
TW200417452A (en) 2004-09-16
CN1325455C (zh) 2007-07-11
TWI312721B (en) 2009-08-01
RU2003134293A (ru) 2005-06-10
RU2340591C2 (ru) 2008-12-10
ITMI20022522A1 (it) 2004-05-29
ES2436041T3 (es) 2013-12-26
KR101086652B1 (ko) 2011-11-24
CN1510019A (zh) 2004-07-07
EP1424320A1 (en) 2004-06-02

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